JP2001286730A - Method for decomposing chlorinated organic compound and method for treating combustion exhaust gas - Google Patents
Method for decomposing chlorinated organic compound and method for treating combustion exhaust gasInfo
- Publication number
- JP2001286730A JP2001286730A JP2000104904A JP2000104904A JP2001286730A JP 2001286730 A JP2001286730 A JP 2001286730A JP 2000104904 A JP2000104904 A JP 2000104904A JP 2000104904 A JP2000104904 A JP 2000104904A JP 2001286730 A JP2001286730 A JP 2001286730A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- chlorinated organic
- organic compound
- tio
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000002485 combustion reaction Methods 0.000 title claims description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 174
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 67
- 238000007254 oxidation reaction Methods 0.000 claims description 55
- 230000003647 oxidation Effects 0.000 claims description 54
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 50
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 47
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 45
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 45
- 229910021529 ammonia Inorganic materials 0.000 claims description 33
- 238000000354 decomposition reaction Methods 0.000 claims description 29
- 239000011218 binary composite Substances 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000004480 active ingredient Substances 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000002013 dioxins Chemical class 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 235000011130 ammonium sulphate Nutrition 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic chlorine compound Chemical class 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 6
- 239000010813 municipal solid waste Substances 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- OGBQILNBLMPPDP-UHFFFAOYSA-N 2,3,4,7,8-Pentachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C=C2C2=C1C=C(Cl)C(Cl)=C2 OGBQILNBLMPPDP-UHFFFAOYSA-N 0.000 description 1
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- GDRNNORFRGCNGA-UHFFFAOYSA-N 2-chloro-1-benzofuran Chemical compound C1=CC=C2OC(Cl)=CC2=C1 GDRNNORFRGCNGA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩素化有機化合物
の分解方法および燃焼排ガスの処理方法に関するもので
あり、詳しくは、低温度でダイオキシン等の塩素化有機
化合物を高効率で分解することが出来る塩素化有機化合
物の分解方法および当該分解方法を特定条件下に利用す
る燃焼排ガスの処理方法に関するものである。The present invention relates to a method for decomposing chlorinated organic compounds and a method for treating flue gas. More specifically, the present invention relates to a method for decomposing chlorinated organic compounds such as dioxin at a low temperature with high efficiency. The present invention relates to a method for decomposing chlorinated organic compounds, and a method for treating combustion exhaust gas using the decomposition method under specific conditions.
【０００２】[0002]
【従来の技術】都市ゴミや産業廃棄物を処理する焼却炉
などから排出される燃焼排ガスは、各種の有害成分を含
有しているが、毒性の強いダイオキシンとその前駆体で
ある芳香族塩素化合物などの塩素化有機化合物および光
化学スモッグの原因物質である窒素酸化物の除去は、特
に重要である。2. Description of the Related Art Combustion exhaust gas discharged from incinerators for treating municipal garbage and industrial waste contains various harmful components, but is highly toxic dioxin and its precursor, an aromatic chlorine compound. Of particular importance is the removal of chlorinated organic compounds such as nitrogen oxides, which are the causative agents of photochemical smog.
【０００３】燃焼排ガス中の塩素化有機化合物の除去方
法としては、各種の方法が知られているが、特に接触分
解法は、５００℃以下の条件で塩素化有機化合物を分解
する優れた方法である。ところで、塩素化有機化合物の
接触分解は、３００℃以上の分解温度では一旦分解され
たダイオキシン等が再生成するため、２５０℃以下の温
度で行うことが要求されている。Various methods are known for removing chlorinated organic compounds from combustion exhaust gas. Particularly, the catalytic cracking method is an excellent method for decomposing chlorinated organic compounds at 500 ° C. or lower. is there. By the way, the catalytic decomposition of chlorinated organic compounds is required to be performed at a temperature of 250 ° C. or less because once decomposed dioxin and the like are regenerated at a decomposition temperature of 300 ° C. or more.
【０００４】更に近年、都市ゴミ焼却設備では、ゴミ焼
却時に発生した熱を回収する目的で得たスチームで発電
し、都市ゴミ焼却設備に電力供給すると共に余剰電力の
売電が行なわれている。ところで、塩素化有機化合物分
解用触媒層の反応温度の維持に上記のスチームが利用さ
れている場合、反応温度が高い程に多量のスチームが消
費される不利益がある。従って、斯かる観点からも可及
的に低い反応温度、具体的には２００℃以下の反応温度
での運転が要求されている。[0004] In recent years, in municipal garbage incineration facilities, power generated by steam obtained for the purpose of recovering heat generated during garbage incineration has been supplied to municipal garbage incineration facilities and surplus power has been sold. By the way, when the above-mentioned steam is used for maintaining the reaction temperature of the chlorinated organic compound decomposition catalyst layer, there is a disadvantage that a larger amount of steam is consumed as the reaction temperature is higher. Therefore, from such a viewpoint, operation at a reaction temperature as low as possible, specifically, a reaction temperature of 200 ° C. or lower is required.
【０００５】一方、塩素化有機化合物の接触分解は、酸
化反応と考えられ、反応温度が低下すると反応速度が必
然的に低下する。従って、より低い温度で接触分解を行
って所定の分解率を得ようとした場合は、触媒量の増加
や単位時間当たりの処理ガス量の低下が必要となる。し
かしながら、都市ゴミ焼却設備では、処理ガス量の低下
が困難なため、処理装置が巨大化するという問題があ
る。[0005] On the other hand, the catalytic decomposition of chlorinated organic compounds is considered to be an oxidation reaction. When the reaction temperature decreases, the reaction rate necessarily decreases. Therefore, when an attempt is made to obtain a predetermined cracking rate by performing catalytic cracking at a lower temperature, it is necessary to increase the amount of the catalyst and decrease the amount of the processing gas per unit time. However, in the municipal garbage incineration equipment, there is a problem that the processing apparatus becomes huge because it is difficult to reduce the amount of processing gas.
【０００６】一方、触媒の担体としては、一般的に、Ｔ
ｉＯ2、ＳｉＯ2、Ａｌ2Ｏ3、ＺｒＯ 2等が使用できる
が、塩素化有機化合物分解用触媒の場合は、燃焼排ガス
中にＳＯ2が含有されている場合が多いため、ＳＯ2に耐
性を有するＴｉＯ2が一般的に使用される。例えば、特
許第２６３３３１６号公報においてはＴｉＯ2担体に活
性成分Ｖ2Ｏ5とＷＯ3を担持した触媒が使用され、特許
第２９１６２５９号公報においては、担体として、Ｔ
ｉ、Ｓｉ、Ｚｒの２元または３元複合酸化物を使用する
ことにより活性成分の分散性を向上させて触媒性能の向
上を図っている。On the other hand, as a carrier for the catalyst, generally, T
iOTwo, SiOTwo, AlTwoOThree, ZrO TwoEtc. can be used
However, in the case of a catalyst for decomposing chlorinated organic compounds,
SO inTwoIs often contained, so SOTwoResistant to
TiO with propertiesTwoIs commonly used. For example,
No. 2633316 discloses TiOTwoActive in carrier
Sexual component VTwoOFiveAnd WOThreeIs used and a patent is used
In Japanese Patent No. 2916259, as a carrier, T
Uses a binary or ternary composite oxide of i, Si, and Zr
This improves the dispersibility of the active ingredients and improves catalyst performance.
I'm aiming up.
【０００７】そして、特許第２６３３３１６号公報にお
いては、２７０〜２９０℃の反応温度が採用されている
が、斯かる温度は十分に低温とは言い難く、また、特許
第２９１６２５９号公報においては、温度が２００℃で
ＳＶが２０００ｈｒ-1の反応条件が採用されており、多
量の触媒を使用する必要がある。[0007] In Japanese Patent No. 2633316, a reaction temperature of 270 to 290 ° C is adopted, but such a temperature is hardly sufficiently low. However, a reaction condition of 200 ° C. and an SV of 2000 hr −1 is adopted, and it is necessary to use a large amount of a catalyst.
【０００８】上述の様に、従来の塩素化有機化合物分解
用触媒は、何れも、低温条件で且つコンパクトな処理装
置で使用するには十分に満足し得る性能ではない。[0008] As described above, none of the conventional catalysts for decomposing chlorinated organic compounds has sufficiently satisfactory performance for use in a compact processing apparatus under low-temperature conditions.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記実情に
鑑みなされたものであり、その目的は、ダイオキシン類
の再合成の問題や触媒層の加熱源であるスチームの使用
量の削減の観点から要求される２５０℃以下（好ましく
は２００℃以下）の反応温度を採用し得る、塩素化有機
化合物の分解方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to reduce the amount of dioxin resynthesis and the amount of steam used as a heating source for a catalyst layer. The present invention provides a method for decomposing chlorinated organic compounds, which can employ a reaction temperature of 250 ° C. or lower (preferably 200 ° C. or lower) required from the above.
【００１０】また、本発明の他の目的は、上記の塩素化
有機化合物の分解方法を特定条件下に利用した燃焼排ガ
スの処理方法であって、しかも、窒素酸化物の分解のた
めに排ガス中に導入されたアンモニアと排ガス中の二酸
化イオウとによって生成する酸性硫酸アンモニウムの触
媒表面への析出を防止し得る様に改良された燃焼排ガス
の処理方法を提供することにある。[0010] Another object of the present invention is a method for treating combustion exhaust gas utilizing the above-mentioned method for decomposing chlorinated organic compounds under specific conditions. It is an object of the present invention to provide a method for treating combustion exhaust gas which is improved so as to prevent the precipitation of ammonium sulfate which is produced by the ammonia introduced into the exhaust gas and the sulfur dioxide in the exhaust gas on the catalyst surface.
【００１１】[0011]
【課題を解決するための手段】本発明者は、種々検討を
重ねた結果、次の様な種々の知見を得た。すなわち、Ｓ
ｉＯ2が高分散しているＳｉＯ2−ＴｉＯ2２元系複合酸
化物と純粋なＴｉＯ2との混合物を担体とする触媒は、
塩素化有機化合物の分解性能が著しく高い。就中、２０
０℃以下の低い反応温度において高い分解性能を示す。
しかも、斯かる担体は、耐ＳＯ2性が高いため、酸性硫
安生成条件下で使用しても性能劣化が小さい。更に、特
定性能の２種類の触媒を特定条件下に使用するならば、
酸性硫酸アンモニウムの触媒表面への析出を防止し得
る。The present inventor has made various studies and obtained the following various findings. That is, S
A catalyst that uses a mixture of a SiO 2 —TiO 2 binary composite oxide in which iO 2 is highly dispersed and pure TiO 2 as a carrier,
Decomposition performance of chlorinated organic compounds is remarkably high. Especially, 20
It shows high decomposition performance at a low reaction temperature of 0 ° C. or less.
In addition, since such a carrier has high resistance to SO 2, its performance is less deteriorated even when used under acidic ammonium sulfate producing conditions. Furthermore, if two types of catalysts with specific performance are used under specific conditions,
It can prevent precipitation of ammonium acid sulfate on the catalyst surface.
【００１２】本発明は、上記の知見に基づき完成された
ものであり、その第１の要旨は、塩素化有機化合物含有
ガスを触媒と接触させる塩素化有機化合物の分解方法に
おいて、担体に活性成分が担持された触媒であって、担
体がＳｉＯ2−ＴｉＯ2２元系複合酸化物とＴｉＯ2から
成り且つ両者の全量に対する前者の割合が５０重量％以
下である混合物から成る触媒を使用することを特徴とす
る塩素化有機化合物の分解方法に存する。The present invention has been completed based on the above findings, and a first gist of the present invention is to provide a method for decomposing a chlorinated organic compound by bringing a gas containing the chlorinated organic compound into contact with a catalyst. Is used, wherein the carrier comprises a mixture of SiO 2 —TiO 2 binary composite oxide and TiO 2 and the ratio of the former to the total amount of both is 50% by weight or less. And a method for decomposing chlorinated organic compounds.
【００１３】そして、本発明の第２の要旨は、塩素化有
機化合物、二酸化イオウ及び窒素酸化物を含有する燃焼
排ガスの処理方法であって、次の（ａ）〜（ｄ）の条件
を満足することを特徴とする燃焼排ガスの処理方法に存
する。A second aspect of the present invention is a method for treating a combustion exhaust gas containing a chlorinated organic compound, sulfur dioxide and nitrogen oxide, which satisfies the following conditions (a) to (d). And a method for treating combustion exhaust gas.
【００１４】（ａ）触媒として、塩素化有機化合物分解
能とアンモニア存在下における窒素酸化物分解能とを有
し且つ以下に規定する二酸化イオウの酸化転化率が１．
３%以下の低酸化性能触媒（Ｘ）と、担体に活性成分が
担持された触媒であって、担体として、ＳｉＯ2−Ｔｉ
Ｏ2２元系複合酸化物とＴｉＯ2から成り且つ両者の全量
に対する前者の割合が５０重量％以下である混合物が使
用され、しかも、塩素化有機化合物分解能を有し且つ以
下に規定する二酸化イオウの酸化転化率が３．０%以上
の高酸化性能触媒（Ｙ）との２種類を使用する。(A) The catalyst has the ability to decompose chlorinated organic compounds and the ability to decompose nitrogen oxides in the presence of ammonia, and has an oxidation conversion of sulfur dioxide of 1.
3% or lower oxidation performance catalyst (X), a catalyst active ingredient to the carrier is carried, as a carrier, SiO 2 -Ti
A mixture comprising an O 2 binary composite oxide and TiO 2, wherein the ratio of the former to the total amount of both is 50% by weight or less, is used, and has the ability to degrade chlorinated organic compounds and is sulfur dioxide defined below. And a high oxidation performance catalyst (Y) having an oxidation conversion of 3.0% or more.
【００１５】＜二酸化イオウの酸化転化率＞圧力：常
圧、温度：２５０℃、ＳＶ（空間速度）：１８５０Ｈｒ
-1、触媒量：４５０ｍｌの条件下、Ｏ2１０乾体積%，Ｓ
Ｏ2５００ｐｐｍ，Ｈ2Ｏ：１０体積%，Ｎ2バランス量の
組成のガスを触媒が充填された反応管に供給し、反応管
出口のＳＯ3濃度とトータルＳＯXの濃度を求め、次式に
より二酸化イオウの酸化転化率（%）を算出する。<Oxidation conversion of sulfur dioxide> Pressure: normal pressure, temperature: 250 ° C., SV (space velocity): 1850 hr
-1 , catalyst amount: under conditions of 450 ml, O 2 10 dry volume%, S
A gas having a composition of 500 ppm O 2 , H 2 O: 10 vol%, and N 2 balance amount is supplied to the reaction tube filled with the catalyst, and the SO 3 concentration and the total SO X concentration at the reaction tube outlet are determined. To calculate the oxidation conversion (%) of sulfur dioxide.
【００１６】[0016]
【数２】 （出口ＳＯ3濃度／出口トータルＳＯX）×１００## EQU2 ## (Outlet SO 3 concentration / Outlet total SO X ) × 100
【００１７】（ｂ）燃焼排ガスと低酸化性能触媒および
高酸化性能触媒との各接触工程を任意の順序で且つ１０
０〜２５０℃の温度範囲で行う。(B) The steps of contacting the combustion exhaust gas with the low oxidizing performance catalyst and the high oxidizing performance catalyst in an arbitrary order
It is performed in a temperature range of 0 to 250 ° C.
【００１８】（ｃ）低酸化性能触媒との接触工程を先行
させる場合、低酸化性能触媒との接触工程に流入する燃
焼排ガス中にアンモニアを導入するが、その量は当該工
程から流出する燃焼排ガス中のアンモニア濃度が２０ｐ
ｐｍ以下となる量に調節する。(C) In the case where the step of contacting with the catalyst having a low oxidation performance is preceded, ammonia is introduced into the flue gas flowing into the step of contacting with the catalyst having a low oxidation performance. Ammonia concentration is 20p
pm or less.
【００１９】（ｄ）高酸化性能触媒との接触工程を先行
させる場合、低酸化性能触媒との接触工程に流入する燃
焼排ガス中にアンモニアを導入する。(D) In the case where the step of contacting with the catalyst having a high oxidation performance is preceded, ammonia is introduced into the combustion exhaust gas flowing into the step of contacting with the catalyst having a low oxidation performance.
【００２０】[0020]
【発明の実施の形態】先ず、本発明に係る塩素化有機化
合物の分解方法について説明する。この発明において
は、塩素化有機化合物分解用触媒として、担体に活性成
分が担持された触媒であって、担体がＳｉＯ2−ＴｉＯ2
２元系複合酸化物とＴｉＯ2から成り且つ両者の全量に
対する前者の割合が５０重量％以下である混合物から成
る触媒を使用する。上記のＳｉＯ2は特に非晶質である
ことが好ましい。First, a method for decomposing a chlorinated organic compound according to the present invention will be described. In the present invention, as a catalyst for decomposing a chlorinated organic compound, a catalyst in which an active ingredient is supported on a carrier, wherein the carrier is SiO 2 —TiO 2
A catalyst comprising a mixture of a binary composite oxide and TiO 2 and having a ratio of the former to 50% by weight or less based on the total amount of both is used. The above SiO 2 is particularly preferably amorphous.
【００２１】ＳｉＯ2−ＴｉＯ2２元系複合酸化物のチタ
ン源は、塩化チタン、硫酸チタニル、メタチタン酸など
から選択することが出来る。ケイ素源としては、コロイ
ド状シリカ、水ガラス、四塩化ケイ素などの無機系ケイ
素化合物およびテトラエチルシリケート等の有機系ケイ
素化合物から選択することが出来る。そして、ＳｉＯ 2
−ＴｉＯ2２元系複合酸化物は、上記の様なチタン源と
ケイ素源とから得られ、例えば、ＴｉＯ2含量が２０〜
５０重量％の含水チタン酸（ＴｉＯ2の水和物）とシリ
カゾルとを所定割合で混合し、十分に熟成させ後に濾過
し、得られたケーキを乾燥して焼成することにより得る
ことが出来る。SiOTwo-TiOTwoBinary composite oxide tita
Sources are titanium chloride, titanyl sulfate, metatitanic acid, etc.
You can choose from. Colloid is a silicon source
Inorganic silica such as silica silica, water glass and silicon tetrachloride
Organic compounds such as silicon compounds and tetraethyl silicate
Element compounds. And SiO Two
-TiOTwoThe binary composite oxide is composed of the above titanium source and
Obtained from a silicon source, such as TiO.TwoContent 20 ~
50% by weight of hydrous titanic acid (TiOTwoHydrate) and sili
Mix with Kasol at a predetermined ratio, allow to mature sufficiently, and then filter
And obtained by drying and baking the obtained cake
I can do it.
【００２２】一般に、ＳｉＯ2−ＴｉＯ2２元複合酸化物
は、固体酸性を有することが知られており、この性質を
塩素化有機化合物の分解に利用した場合、脱塩素化反応
の促進により分解効率の向上が期待できる。また、一般
に、比表面積や耐ＳＯX性が向上することも期待でき
る。In general, it is known that a binary oxide of SiO 2 —TiO 2 has solid acidity, and when this property is used for decomposing a chlorinated organic compound, it is decomposed by accelerating the dechlorination reaction. Improvement of efficiency can be expected. In general, improvement in specific surface area and SO X resistance can also be expected.
【００２３】しかしながら、酸性硫安の付着により触媒
性能が劣化した場合、通常、反応速度が低下する。酸性
硫安が生成する様な低温反応温度域ではダイオキシン類
は、脱塩素化反応によって分解されることが多いが、脱
塩素化反応の反応速度が低下した場合、毒性の低い８塩
素体のダイオキシン類が反応によって毒性の強い４塩素
体のダイオキシンになることも予想される。従って、酸
性硫安が生成するガス成分やガス温度領域で使用する触
媒に対し、固体酸性のみを付与し、脱塩素化反応の能力
を向上させて塩素化有機化合物の分解率を向上させる方
法は、必ずしも得策ではない。また、最近注目されてい
るコプラナーＰＣＢは、構造内に酸素を持たないことか
ら、よりベンゼン環の酸化分解能力が高い触媒を使用し
ないと所定の分解効率が得られない。However, when the catalytic performance is degraded due to the adhesion of acidic ammonium sulfate, the reaction rate usually decreases. Dioxins are often decomposed by a dechlorination reaction in a low-temperature reaction temperature range in which acidic ammonium sulfate is generated. However, when the reaction rate of the dechlorination reaction is reduced, dioxins of low toxicity are reduced to 8-chlorine dioxins. Is also expected to become a highly toxic 4-chlorinated dioxin by the reaction. Therefore, a method of imparting only solid acidity to a gas component generated by acidic ammonium sulfate or a catalyst used in a gas temperature range, improving the dechlorination reaction ability, and improving the decomposition rate of the chlorinated organic compound, Not always a good idea. In addition, since coplanar PCBs, which have recently attracted attention, have no oxygen in the structure, a predetermined decomposition efficiency cannot be obtained unless a catalyst having a higher ability to oxidize and decompose benzene rings is used.
【００２４】本発明者らは、塩素化有機化合物分解用触
媒の評価方法として、代替物質の分解率によって評価す
る場合、構造内に酸素を有する芳香族塩素化合物、例え
ばｏ−クロルフェノール等の分解性能は、脱塩素化反応
による分解性能（主に低温反応でのダイオキシン類の分
解性能）と対応し、構造内に酸素を有しない芳香族塩素
化合物、例えばモノクロルベンゼン等の分解性能は、酸
化分解反応による分解性能（主にコプラナーＰＣＢ分解
性能）と対応することを知見として得ている。As a method for evaluating a catalyst for decomposing chlorinated organic compounds, the present inventors have proposed a method for decomposing an aromatic chlorine compound having oxygen in its structure, for example, o-chlorophenol, when evaluating the decomposition rate of a substitute substance. The performance corresponds to the decomposition performance by the dechlorination reaction (mainly the decomposition performance of dioxins in low-temperature reactions), and the decomposition performance of aromatic chlorine compounds without oxygen in the structure, such as monochlorobenzene, is determined by oxidative decomposition. It is obtained as knowledge that it corresponds to the decomposition performance by the reaction (mainly the coplanar PCB decomposition performance).
【００２５】本発明者らの検討の結果によれば、２００
℃以下の低温反応領域で酸化分解性能を低下させずに、
ＳｉＯ2の添加による効果、例えば、耐ＳＯx性の向上、
脱塩素化反応の促進、脱硝反応性能の向上などを引き出
す方法として、ＳｉＯ2−ＴｉＯ2２元系複合酸化物とＴ
ｉＯ2とを両者の全量に対する前者の割合が５０重量％
以下となる様に混合する方法が有力である。According to the results of the study by the present inventors, 200
Without lowering the oxidative decomposition performance in the low temperature reaction zone below ℃
Effect of addition of SiO 2 , for example, improvement of SO x resistance,
As a method for accelerating the dechlorination reaction and improving the performance of the denitration reaction, SiO 2 —TiO 2 binary composite oxide and T
50% by weight of iO 2 with respect to the total amount of both
The method of mixing as follows is effective.
【００２６】更に、本発明者らの検討の結果によれば、
上記の方法で得られる混合物において、形成助材として
使用されることがある石英繊維などのＳｉＯ2を除き、
ＳｉＯ2の割合が０．５〜３重量％であり、残余がＴｉ
Ｏ2である様に濃度調整することにより、高酸化活性能
・高脱塩素活性能の触媒を調製することが出来る。Further, according to the results of the study by the present inventors,
In the mixture obtained by the above method, except for SiO 2 such as quartz fiber that may be used as a forming aid,
The proportion of SiO 2 is 0.5 to 3% by weight, and the balance is Ti
By adjusting the concentration so as to be O 2 , a catalyst having high oxidizing activity and high dechlorinating activity can be prepared.
【００２７】上記のＳｉＯ2−ＴｉＯ2２元系複合酸化物
において、ＳｉＯ2含有量は、通常１〜２０重量％、好
ましくは２〜１５重量％である。ＳｉＯ2含有量が１重
量％未満の場合はＳｉＯ2の高分散による前述効果が現
れず、ＳｉＯ2含有量が２０重量％を超える場合は高分
散が困難となる。In the above-mentioned SiO 2 —TiO 2 binary composite oxide, the SiO 2 content is usually 1 to 20% by weight, preferably 2 to 15% by weight. If SiO 2 content is less than 1 wt% not appear above effect due to the high dispersion of SiO 2, a high dispersion becomes difficult if the SiO 2 content exceeds 20% by weight.
【００２８】ＴｉＯ2にＳｉＯ2が非晶質で高分散してい
るか否かの確認は、以下に説明する様にＸ線回折によっ
て行なうことが出来る。すなわち、Ｘ線回折スペクトル
において、ピーク強度はＳｉＯ2の含有量によって変化
するが、ＳｉＯ2の分散性が悪くＳｉＯ2結晶が存在する
場合は２θ＝２６．６°の位置にピークが出現する。逆
に、ＳｉＯ2が多量に存在する場合でもＳｉＯ2が高分散
しているＳｉＯ2−ＴｉＯ2２元系複合酸化物の場合は、
２θ＝２６．６°の位置にピークは出現せず、試薬特級
のアナターゼ型ＴｉＯ2と同じ位置にのみピークが出現
する。Whether or not SiO 2 is amorphous and highly dispersed in TiO 2 can be confirmed by X-ray diffraction as described below. That is, in the X-ray diffraction spectrum, the peak intensity varies depending on the content of SiO 2, if the dispersibility of SiO 2 is SiO 2 crystals are present poor peak appears at the position of 2θ = 26.6 °. Conversely, in the case of SiO 2 -TiO 2 2-element composite oxides SiO 2, even if the SiO 2 is present in large quantities are highly dispersed,
No peak appears at the position of 2θ = 26.6 °, and a peak appears only at the same position as the reagent-grade anatase-type TiO 2 .
【００２９】本発明において、塩素化有機化合物分解触
媒の活性成分は、通常、Ｖ、Ｃｒ、Ｍｏ、Ｍｎ、Ｆｅ、
Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、Ｎｄ、Ｗ、
Ｉｎ及びＩｒの群から選ばれる少なくとも１種の金属お
よび／またはその酸化物である。これらの中では、バナ
ジウム（Ｖ）酸化物が安価であり且つ塩素化有機化合物
の分解率が高いために好適に使用される。In the present invention, the active components of the chlorinated organic compound decomposition catalyst are usually V, Cr, Mo, Mn, Fe,
Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, W,
At least one metal selected from the group consisting of In and Ir and / or an oxide thereof. Among these, vanadium (V) oxide is preferably used because it is inexpensive and has a high decomposition rate of chlorinated organic compounds.
【００３０】活性成分としてバナジウム酸化物を使用す
る場合、ＭｏＯ3やＷＯ3でＶ2Ｏ5を修飾することにより
Ｖ2Ｏ5の分散性が向上して活性が向上することが知られ
ている。しかしながら、塩素化有機化合物分解用触媒に
おいては、単純に酸化活性を向上させてしまうとＳＯ2
の酸化活性も向上し、その結果、酸性硫安の生成が促進
され、ひいては、触媒性能の劣化が促進される。また、
ＭｏＯ3の添加は、酸化活性を抑制するが、塩素化有機
化合物の分解活性も抑制する。When vanadium oxide is used as an active ingredient, it is known that by modifying V 2 O 5 with MoO 3 or WO 3 , the dispersibility of V 2 O 5 is improved and the activity is improved. . However, in the chlorinated organic compound decomposition catalyst, if the oxidation activity is simply improved, SO 2
The oxidation activity of the catalyst is also improved, and as a result, the production of acidic ammonium sulfate is promoted, and the deterioration of the catalyst performance is promoted. Also,
The addition of MoO 3 suppresses the oxidizing activity but also suppresses the decomposition activity of the chlorinated organic compound.
【００３１】しかしながら、本発明者らの検討の結果に
よれば、Ｖ2Ｏ5量が触媒量に対し５重量以上で且つＭｏ
Ｏ3量がＶ2Ｏ5に対し１〜２倍モルに調整された活性成
分を前記の担体に担持して成る触媒の場合は、上記の性
質とは全く異なり、塩素化有機化合物の酸化分解性能が
向上し、しかも、ＳＯ2酸化性能が抑制され且つ酸性硫
安による性能劣化が軽減される。斯かる効果は、バナジ
ウムとモリブデンの複合酸化物の生成に起因していると
考えられる。However, according to the results of the study by the present inventors, the amount of V 2 O 5 was 5 wt.
In the case of a catalyst in which the active component whose O 3 amount is adjusted to 1 to 2 times the mole of V 2 O 5 is supported on the above-described carrier, the oxidative decomposition of the chlorinated organic compound is completely different from the above properties. The performance is improved, the SO 2 oxidation performance is suppressed, and the performance deterioration due to acidic ammonium sulfate is reduced. Such an effect is considered to be caused by the formation of a composite oxide of vanadium and molybdenum.
【００３２】上記のバナジウム酸化物の原料としては、
特に制限されないが、五酸化バナジウム（Ｖ2Ｏ5）又は
メタバナジン酸アンモニウム（ＮＨ4ＶＯ3）が好適に使
用される。これらの原料は、通常、シュウ酸水溶液また
はモノエタノールアミン水溶液に溶解して原料液として
使用される。モリブデン酸化物の原料としては、特に制
限されないが、パラモリブデン酸アンモニウムが好適に
使用される。これらの原料は、通常、熱水またはエタノ
ールアミン水溶液に溶解して使用される。塩素化有機化
合物分解触媒中のバナジウム酸化物の含有量は、活性成
分として単独使用する他、触媒の使用方法などによって
異なるが、通常０．１〜３０重量％、好ましくは５〜２
０重量％である。As a raw material of the above-mentioned vanadium oxide,
Although not particularly limited, vanadium pentoxide (V 2 O 5 ) or ammonium metavanadate (NH 4 VO 3 ) is preferably used. These raw materials are usually used as a raw material liquid by dissolving in an oxalic acid aqueous solution or a monoethanolamine aqueous solution. The material for the molybdenum oxide is not particularly limited, but ammonium paramolybdate is preferably used. These raw materials are usually used after being dissolved in hot water or an aqueous solution of ethanolamine. The content of vanadium oxide in the chlorinated organic compound decomposition catalyst may vary depending on the method of using the catalyst, besides being used alone as the active ingredient, but is usually 0.1 to 30% by weight, preferably 5 to 2%.
0% by weight.
【００３３】上記の金属活性成分を使用する場合、活性
成分の水溶液と担体とをよく混合して成形した後に焼成
するか、成形した担体基材に活性成分の水溶液を含浸さ
せた後に焼成する方法により、触媒を調製する。そし
て、例えば銅を使用する場合は、硝酸銅を水に溶解して
活性成分の水溶液を調製する。When the above-mentioned metal active component is used, a method of baking after mixing the aqueous solution of the active component and the carrier well and molding, or impregnating the molded carrier substrate with the aqueous solution of the active component and then calcining. To prepare a catalyst. When copper is used, for example, copper nitrate is dissolved in water to prepare an aqueous solution of the active ingredient.
【００３４】また、触媒の形状および大きさは、塩素化
有機化合物含有ガス中におけるダストの有無、処理ガス
量、反応器の大きさ等により、適宜選択される。触媒の
形状としては、ハニカム状、円柱状、球状、板状などが
挙げられる。The shape and size of the catalyst are appropriately selected depending on the presence or absence of dust in the chlorinated organic compound-containing gas, the amount of processing gas, the size of the reactor, and the like. Examples of the shape of the catalyst include a honeycomb shape, a column shape, a spherical shape, and a plate shape.
【００３５】担体に活性成分が担持されたハニカム形状
の触媒を製造する方法として、（ａ）担体成分と活性成
分またはその原料を成形助材と共に混練した後に、押出
成形法など によりハニカム状の形状に賦形する方法、
（ｂ）ハニカム形状の基材上に担体成分および活性成分
を含浸・担持する方法を挙げることが出来る。上述の製
造方法（ａ）の１例として、以下の方法が例示される。As a method for producing a honeycomb-shaped catalyst in which an active component is supported on a carrier, (a) the carrier component and the active component or the raw material thereof are kneaded together with a forming aid, and then the honeycomb-shaped catalyst is extruded. How to shape into
(B) a method of impregnating and supporting a carrier component and an active component on a honeycomb-shaped substrate. As an example of the above-mentioned manufacturing method (a), the following method is exemplified.
【００３６】（１）メタバナジン酸アンモニウムを約１
０重量％モノエタノールアミン水溶液に溶解する。 （２）硫酸チタン溶液を熱加水分解してメタチタン酸ス
ラリーを得る。 （３）メタチタン酸スラリーに１５重量％アンモニア水
を加えてｐＨ調整した後、リフラックス処理を１時間以
上行なう。 （４）シリカゾルを加え、更に、リフラックス処理を１
時間以上行なう。 （５）得られたスラリーを濾過し、得られたケーキを５
０〜１５０℃の温度で３〜５０時間乾燥した後、４００
〜６５０℃の温度で焼成し、冷却後に粉砕する。 （６）得られた粉末状のＳｉＯ2−ＴｉＯ2２元系複合酸
化物を５０重量％以下の割合のＴｉＯ2と混合して担体
とする。 （７）上記の担体と上記の（１）で調製した水溶液とを
ニーダーで混練する。(1) Ammonium metavanadate is added to about 1
Dissolve in 0% by weight monoethanolamine aqueous solution. (2) The titanium sulfate solution is thermally hydrolyzed to obtain a metatitanic acid slurry. (3) After adding 15% by weight of aqueous ammonia to the metatitanic acid slurry to adjust the pH, a reflux treatment is performed for 1 hour or more. (4) Add silica sol, and further perform reflux treatment for 1
Perform for more than an hour. (5) The obtained slurry is filtered, and the obtained cake is
After drying at a temperature of 0 to 150 ° C. for 3 to 50 hours, 400
Bake at a temperature of ６650 ° C. and pulverize after cooling. (6) The obtained powdery SiO 2 —TiO 2 binary composite oxide is mixed with TiO 2 in a proportion of 50% by weight or less to prepare a carrier. (7) The above carrier and the aqueous solution prepared in the above (1) are kneaded with a kneader.
【００３７】（８）（ｉ）更に成形助材を加えて混練し
た混練物を押出成形し、５０〜１５０℃の温度で３〜５
０時間乾燥した後、ＳＶ１００〜２０００Ｈｒ-1の空気
気流中、４５０〜６５０℃の温度で焼成する、または
（ ii ）混練物を５０〜１５０℃の温度で３〜５０時間
乾燥し、４５０〜６５０℃の温度で焼成した後、成形助
材を加えて成形する。(8) (i) A kneaded product obtained by further kneading with the addition of a molding aid is extruded, and is extruded at a temperature of 50 to 150 ° C. for 3 to 5
After drying for 0 hour, the mixture is calcined at a temperature of 450 to 650 ° C. in an air stream of SV 100 to 2000 Hr −1 , or (ii) the kneaded material is dried at a temperature of 50 to 150 ° C. for 3 to 50 hours. After baking at a temperature of ° C., a molding aid is added and molded.
【００３８】また、上述の製造方法（ｂ）の１例とし
て、次の方法が例示される。すなわち、円柱状、球状、
ハニカム状、板状など 、所望の形状の基材上に上記の
（２）〜（６）で調製した担体成分をコーティングし、
上記の（１）で調製した水溶液を塗布して活性成分を含
浸させ、５０〜１５０℃で３〜５０時間乾燥した後、４
５０〜６５０℃の温度で焼成する。As an example of the above-mentioned manufacturing method (b), the following method is exemplified. That is, cylindrical, spherical,
The carrier component prepared in the above (2) to (6) is coated on a substrate having a desired shape such as a honeycomb shape or a plate shape,
The aqueous solution prepared in the above (1) is applied to impregnate the active ingredient, dried at 50 to 150 ° C. for 3 to 50 hours, and then dried.
Baking at a temperature of 50 to 650 ° C.
【００３９】基材上に形成された触媒の場合、基材とし
ては、ＴｉＯ2に、シリカ（ＳｉＯ2）やアルミナ（Ａｌ
2Ｏ3）等を単独で又は併用して使用する。ＳｉＯ2−Ｔ
ｉＯ2２元系複合酸化物とＴｉＯ2との混合物（担体成
分）の量は、担体成分と活性成分との合計量に対し、通
常７０〜９９重量％である。また、担体成分と活性成分
との合計量は、基材、担体成分および活性成分の総量に
対し、通常５〜７０重量％、好ましくは１０〜５０重量
％である。In the case of a catalyst formed on the substrate, as the substrate, the TiO 2, silica (SiO 2) or alumina (Al
2 O 3 ) and the like are used alone or in combination. SiO 2 -T
The amount of iO 2 2-element complex oxide and a mixture of TiO 2 (carrier component), the total amount of the carrier component and the active ingredient is usually 70 to 99 wt%. The total amount of the carrier component and the active ingredient is usually 5 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of the base material, the carrier component and the active ingredient.
【００４０】混練・成形方法の様に添加した原料が全て
活性成分となる場合は、それぞれの金属塩など の原料
成分が対応する金属酸化物に変化したものとして、触媒
組成は添加量から推算する。また、含浸方法で製造され
た場合は、触媒をフッ化水素酸で処理した後、硫酸アン
モニウムで融解してプラズマ発光分析法（ＩＣＰ−ＡＥ
Ｓ分析法）により触媒組成を測定する。When the raw materials added are all active ingredients as in the kneading and molding method, the catalyst composition is estimated from the added amount on the assumption that the raw material components such as metal salts have changed to the corresponding metal oxides. . When the catalyst is manufactured by the impregnation method, the catalyst is treated with hydrofluoric acid, then melted with ammonium sulfate, and plasma emission spectrometry (ICP-AE) is performed.
S analysis) to determine the catalyst composition.
【００４１】本発明に係る塩素化有機化合物の分解方法
は、塩素化有機化合物含有ガスを上記の触媒と接触させ
る。塩素化有機化合物含有ガスとしては、例えば、２，
３，７，８−テトラクロロジベンゾダイオキシン及び
２，３，４，７，８−ぺンタクロロジベンゾフランで代
表されるダイオキシン類や３，３’，４，４’，５−ペ
ンタクロロビフェニルで代表されるコプラナーＰＣＢ類
が約０．１〜２００ｎｇ／ｍ3（Ｎ．Ｔ．Ｐ）（毒性等
価換算値）含有され、更に、ダイオキシン類の前駆体物
質である、モノクロロベンゼン、トリクロロベンゼン等
のクロロベンゼン類、Ｏ−クロロフェノール、トリクロ
ロフェノール等のクロロフェノール類、クロロベンゾフ
ラン等が含有されたガス、具体的には、後述する燃焼排
ガスの処理方法における都市ごみや産業廃棄物などを燃
焼した際の排ガス等が挙げられる。斯かる塩素化有機化
合物含有ガスは、水分と共に酸素を含有し、その含有量
は、通常０．５〜２５ｖｏｌ％、好ましく１〜２１ｖｏ
ｌ％である。In the method for decomposing a chlorinated organic compound according to the present invention, a gas containing a chlorinated organic compound is brought into contact with the above-mentioned catalyst. As the chlorinated organic compound-containing gas, for example, 2,
Dioxins represented by 3,7,8-tetrachlorodibenzodioxin and 2,3,4,7,8-pentachlorodibenzofuran and represented by 3,3 ', 4,4', 5-pentachlorobiphenyl Chlorobenzenes such as monochlorobenzene and trichlorobenzene, which are co-planar PCBs containing about 0.1 to 200 ng / m 3 (NTP) (equivalent value in terms of toxicity). , A gas containing chlorophenols such as O-chlorophenol and trichlorophenol, chlorobenzofuran, etc., and more specifically, an exhaust gas when burning municipal solid waste or industrial waste in a method for treating a combustion exhaust gas described below. Is mentioned. Such a chlorinated organic compound-containing gas contains oxygen together with water, and its content is usually 0.5 to 25 vol%, preferably 1 to 21 vol.
1%.
【００４２】上記の様な塩素化有機化合物含有ガスは、
通常、バッグフィルターに通じて粉塵や重金属などを除
去した後に接触工程に導入される。また、必要に応じ、
バッグフィルターで処理する前に消石灰反応塔で処理し
て酸性ガスを除去してもよい。The chlorinated organic compound-containing gas as described above is
Usually, it is introduced into the contact step after removing dust and heavy metals through a bag filter. Also, if necessary,
Before the treatment with the bag filter, the treatment may be performed in a slaked lime reaction tower to remove the acidic gas.
【００４３】塩素化有機化合物含有ガスと触媒との接触
温度は、通常１００〜２５０℃、好ましくは１００〜２
００℃である。接触温度が２５０℃を超える場合は、塩
素化有機化合物の分解率も増加するが、分解されたダイ
オキシン類が再合成する問題と共に触媒層加熱用スチー
ムの節約の観点からも不利である。接触温度が１００℃
未満の場合は、運転上支障を来す結露が惹起される。触
媒層の圧力は、ゲージ圧として、通常−０．０５〜０．
９ＭＰａ、好ましくは−０．０１〜０．５ＭＰａであ
る。また、空間速度（ＳＶ）は、通常１００〜５０００
０Ｈｒ-1、好ましくは１０００〜２００００Ｈｒ-1であ
る。The contact temperature between the chlorinated organic compound-containing gas and the catalyst is usually 100 to 250 ° C., preferably 100 to 250 ° C.
00 ° C. When the contact temperature exceeds 250 ° C., the decomposition rate of the chlorinated organic compound also increases, but this is disadvantageous from the viewpoint of re-synthesizing the decomposed dioxins and saving steam for heating the catalyst layer. Contact temperature is 100 ℃
If it is less than the above range, dew condensation which causes trouble in operation is caused. The pressure of the catalyst layer is usually -0.05 to 0.1 as a gauge pressure.
It is 9 MPa, preferably -0.01 to 0.5 MPa. The space velocity (SV) is usually 100 to 5000
0Hr -1, preferably 1000~20000Hr -1.
【００４４】次に、本発明に係る燃焼排ガスの処理方法
について説明する。この発明においては、触媒として、
塩素化有機化合物分解能とアンモニア存在下における窒
素酸化物分解能とを有し且つ以下に規定する二酸化イオ
ウの酸化転化率が１．３%以下の低酸化性能触媒（Ｘ）
と、担体に活性成分が担持された触媒であって、担体と
して、ＳｉＯ2−ＴｉＯ2２元系複合酸化物とＴｉＯ2か
ら成り且つ両者の全量に対する前者の割合が５０重量％
以下である混合物が使用され、しかも、塩素化有機化合
物分解能を有し且つ以下に規定する二酸化イオウの酸化
転化率が３．０%以上の高酸化性能触媒（Ｙ）との２種
類を使用する。Next, a method for treating combustion exhaust gas according to the present invention will be described. In the present invention, as a catalyst,
Low oxidation performance catalyst (X) having a chlorinated organic compound resolution and a nitrogen oxide resolution in the presence of ammonia, and having an oxidation conversion of sulfur dioxide of 1.3% or less as defined below (X)
And a catalyst in which an active component is supported on a carrier, wherein the carrier is composed of a SiO 2 —TiO 2 binary composite oxide and TiO 2 , and the ratio of the former to the total amount of both is 50% by weight.
The following mixture is used, and a high oxidation performance catalyst (Y) having a chlorinated organic compound decomposability and an oxidation conversion of sulfur dioxide of 3.0% or more as defined below is used. .
【００４５】＜二酸化イオウの酸化転化率＞圧力：常
圧、温度：２５０℃、ＳＶ（空間速度）：１８５０Ｈｒ
-1、触媒量：４５０ｍｌの条件下、Ｏ2１０乾体積%，Ｓ
Ｏ2５００ｐｐｍ，Ｈ2Ｏ：１０体積%，Ｎ2バランス量の
組成のガスを触媒が充填された反応管に供給し、反応管
出口のＳＯ3濃度とトータルＳＯXの濃度を求め、次式に
より二酸化イオウの酸化転化率（%）を算出する。<Oxidation conversion of sulfur dioxide> Pressure: normal pressure, temperature: 250 ° C., SV (space velocity): 1850 hr
-1 , catalyst amount: under conditions of 450 ml, O 2 10 dry volume%, S
A gas having a composition of 500 ppm O 2 , H 2 O: 10 vol%, and N 2 balance amount is supplied to the reaction tube filled with the catalyst, and the SO 3 concentration and the total SO X concentration at the reaction tube outlet are determined. To calculate the oxidation conversion (%) of sulfur dioxide.
【００４６】[0046]
【数３】 （出口ＳＯ3濃度／出口トータルＳＯX）×１００[Equation 3] (Outlet SO 3 concentration / Outlet total SO X ) × 100
【００４７】上記の様に規定された低酸化性能触媒
（Ｘ）は、排ガス中にアンモニアと二酸化イオウ（実際
は硫黄酸化物ＳＯXとＨ2Ｏ）が存在する場合において、
ＳＯ2やＳＯ3が物理的に吸着することはあっても、酸性
硫酸アンモニウムを殆ど生成しない特徴を有する。とこ
ろで、通常、二酸化イオウの酸化転化率が低い触媒は、
塩素化有機化合物の分解性能が低い。従って、低酸化性
能触媒（Ｘ）のみを使用した場合は、大量の触媒が塩素
化有機化合物の高い除去率のために必要となり、効率が
悪くなる。The low oxidizing performance catalyst (X) defined as described above can be used when ammonia and sulfur dioxide (actually, sulfur oxides SO X and H 2 O) are present in the exhaust gas.
Although SO 2 and SO 3 are physically adsorbed, they have a characteristic that they hardly generate ammonium ammonium sulfate. By the way, usually, a catalyst having a low oxidation conversion of sulfur dioxide is
Decomposition performance of chlorinated organic compounds is low. Therefore, when only the low oxidation performance catalyst (X) is used, a large amount of the catalyst is required for a high removal rate of the chlorinated organic compound, and the efficiency is deteriorated.
【００４８】そこで、本発明においては、上記の様に規
定された高酸化性能触媒（Ｙ）、すなわち、塩素化有機
化合物の分解性能が高い触媒を使用することにより、換
言すれば、本発明に係る塩素化有機化合物の分解方法を
特定条件下に利用する（本発明に係る塩素化有機化合物
分解用触媒を二酸化イオウの酸化転化率３．０%以上に
修飾して利用する）ことにより、トータルとして比較的
少量の触媒量で塩素化有機化合物の高い除去率を達成し
ている。そして、高酸化性能触媒（Ｙ）の場合は、排ガ
ス中にアンモニアと二酸化イオウが存在すると、１００
〜２５０℃の温度において、酸性硫酸アンモニウムが生
成して触媒表面に付着して性能低下を惹起する。従っ
て、高酸化性能触媒（Ｙ）は、後述する通り、燃焼排ガ
ス中のアンモニア濃度が２０ｐｐｍ以下の条件で使用さ
れる。Therefore, in the present invention, by using the high oxidation performance catalyst (Y) defined as described above, that is, a catalyst having high decomposition performance of chlorinated organic compounds, in other words, the present invention By utilizing such a method for decomposing chlorinated organic compounds under specific conditions (using the catalyst for decomposing chlorinated organic compounds according to the present invention modified to an oxidation conversion of sulfur dioxide of 3.0% or more), the total As a result, a high removal rate of chlorinated organic compounds is achieved with a relatively small amount of catalyst. In the case of the high oxidation performance catalyst (Y), if ammonia and sulfur dioxide are present in the exhaust gas, 100%
At a temperature of ℃ 250 ° C., ammonium ammonium sulphate is formed and adheres to the surface of the catalyst, causing a reduction in performance. Therefore, the high oxidation performance catalyst (Y) is used under the condition that the ammonia concentration in the combustion exhaust gas is 20 ppm or less, as described later.
【００４９】低酸化性能触媒（Ｘ）の二酸化イオウの酸
化転化率は、酸性硫酸アンモニウムの生成を一層確実に
防止する観点から０．８%以下が好ましく、高酸化性能
触媒（Ｙ）の二酸化イオウの酸化転化率は、塩素化有機
化合物の除去率を一層高める観点から、５%以上が好ま
しく、６%以上が更に好ましい。The oxidation conversion of sulfur dioxide of the low oxidation catalyst (X) is preferably 0.8% or less from the viewpoint of more reliably preventing the formation of ammonium acid sulfate. The oxidative conversion rate is preferably 5% or more, and more preferably 6% or more, from the viewpoint of further increasing the removal rate of the chlorinated organic compound.
【００５０】上記の二酸化イオウの異なる酸化転化率
は、組成や種類の異なる触媒を使用すること等により達
成することが出来る。例えば、銅酸化物（ＣｕＯ）含有
量が５．０％以下の場合は低酸化性能触媒（Ｘ）、８．
５％以上の場合は高酸化性能触媒（Ｙ）が得られる。ま
た、Ｖ2Ｏ5含有量が２．５重量%以下の場合は低酸化性
能触媒（Ｘ）、３．５重量%以上の場合は高酸化性能触
媒（Ｙ）が得られる。The above-mentioned different oxidation conversion of sulfur dioxide can be achieved by using catalysts having different compositions and types. For example, when the copper oxide (CuO) content is 5.0% or less, the low oxidation performance catalyst (X),
When it is 5% or more, a high oxidation performance catalyst (Y) can be obtained. When the V 2 O 5 content is 2.5% by weight or less, a low oxidation performance catalyst (X) is obtained, and when the V 2 O 5 content is 3.5% by weight or more, a high oxidation performance catalyst (Y) is obtained.
【００５１】先ず、低酸化性能触媒（Ｘ）について説明
する。この触媒は、通常、担体に活性成分を担持して形
成される。担体としては、特に制限されないが、ＳＯX
含有燃焼排ガスを処理する観点から、耐酸性に優れるＴ
ｉＯ2が好適に使用される。ＴｉＯ2としては、ＴｉＯ2
−ＳｉＯ2、ＴｉＯ2−ＳｉＯ2−ＺｒＯ2、ＴｉＯ2−Ｗ
Ｏ3−ＳｉＯ2等の複合酸化物であってもよい。First, the low oxidation performance catalyst (X) will be described. This catalyst is usually formed by supporting an active ingredient on a carrier. Although the carrier is not particularly limited, SO X
From the viewpoint of treating contained flue gas, T
iO 2 is preferably used. As TiO 2 , TiO 2
—SiO 2 , TiO 2 —SiO 2 —ZrO 2 , TiO 2 —W
A composite oxide such as O 3 —SiO 2 may be used.
【００５２】触媒の活性成分としては、前述の塩素化有
機化合物の分解方法におけるのと同様の成分、例えば、
Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ等の遷移金属の酸化物の
他、貴金属、ゼオライト等が挙げられる。これらの内、
バナジウム酸化物、銅酸化物、鉄酸化物および金が好ま
しい。更に、バナジウム酸化物を含有する触媒は、安価
であり、塩素化有機化合物の分解率が高く、しかも、ア
ンモニアの存在下に窒素酸化物が分解できるため、特に
好ましい。バナジウム酸化物の担持量は、上記と同様
に、通常は０．１〜３０重量%、好ましくは０．１〜２
０重量%である。As the active component of the catalyst, the same components as those used in the method for decomposing chlorinated organic compounds described above, for example,
In addition to oxides of transition metals such as V, Cr, Mn, Fe, and Cu, noble metals, zeolites, and the like are included. Of these,
Vanadium oxide, copper oxide, iron oxide and gold are preferred. Further, a catalyst containing vanadium oxide is particularly preferable because it is inexpensive, has a high decomposition rate of a chlorinated organic compound, and can decompose nitrogen oxide in the presence of ammonia. The loading amount of vanadium oxide is usually 0.1 to 30% by weight, preferably 0.1 to 2%, as described above.
0% by weight.
【００５３】また、低酸化性能触媒（Ｘ）としては、上
記の二酸化イオウの酸化転化率の条件を満足する限り、
前記の塩素化有機化合物分解用触媒と同様の触媒を使用
することも出来る。触媒の形状および大きさ、触媒の調
製方法などは、前記の塩素化有機化合物分解用触媒の場
合と同様である。As the low oxidation performance catalyst (X), as long as the above-mentioned condition of the oxidation conversion of sulfur dioxide is satisfied,
A catalyst similar to the above-mentioned catalyst for decomposing chlorinated organic compounds can also be used. The shape and size of the catalyst, the method for preparing the catalyst, and the like are the same as in the case of the catalyst for decomposing chlorinated organic compounds.
【００５４】次に、高酸化性能触媒（Ｙ）について説明
する。この触媒は、既に述べた様に、前記の塩素化有機
化合物分解用触媒を二酸化イオウの酸化転化率３．０%
以上に修飾したものである。Next, the high oxidation performance catalyst (Y) will be described. As described above, this catalyst uses the above catalyst for decomposing chlorinated organic compounds at an oxidative conversion of sulfur dioxide of 3.0%.
The above is a modification.
【００５５】次に、本発明の燃焼排ガスの処理方法につ
いて説明する。本発明においては、燃焼排ガスと低酸化
性能触媒および高酸化性能触媒との各接触工程を任意の
順序で且つ１００〜２５０℃の温度範囲で行う。接触温
度２５０℃以下の条件は、前述の様に分解されたダイオ
キシン等の再生成を防止する観点から規定された条件で
あり、接触温度１００℃以上の条件は、装置の運転に支
障を来す結露を確実に防止する観点から規定された条件
である。接触処理中の圧力は、ゲージ圧で通常−０．０
５〜０．９ＭＰａ、好ましくは−０．０１〜０．５ＭＰ
ａである。また、ＳＶは、通常１００〜５００００Ｈｒ
-1、好ましくは１０００〜２００００Ｈｒ-1である。Next, the method for treating combustion exhaust gas of the present invention will be described. In the present invention, each contacting step between the combustion exhaust gas and the low oxidizing performance catalyst and the high oxidizing performance catalyst is performed in an arbitrary order and in a temperature range of 100 to 250 ° C. The condition at a contact temperature of 250 ° C. or less is a condition defined from the viewpoint of preventing regeneration of decomposed dioxin and the like as described above, and the condition at a contact temperature of 100 ° C. or more hinders the operation of the apparatus. This is a condition specified from the viewpoint of reliably preventing dew condensation. The pressure during the contact treatment is usually -0.0
5 to 0.9 MPa, preferably -0.01 to 0.5 MPa
a. SV is usually 100 to 50,000 Hr.
−1 , preferably 1000 to 20000 Hr −1 .
【００５６】本発明の処理方法が対象とする燃焼排ガス
としては、塩素化有機化合物、通常０．１ｐｐｍ以上の
ＮＯx、通常０．１ｐｐｍ以上のＳＯxを含有する排ガ
ス、例えば都市ごみや産業廃棄物などを燃焼した際の排
ガス等が挙げられる。この様な燃焼排ガスには、水分お
よび酸素と共に、前記のダイオキシン類およびコプラナ
ーＰＣＢ類が０．１〜２００ｎｇ／ｍ3（Ｎ．Ｔ．Ｐ）
（毒性等価換算値）含まれている。更に、前述の通り、
ダイオキシン類の前駆体である種々の塩素化有機化合物
も含まれている。As the combustion exhaust gas to be treated by the treatment method of the present invention, an exhaust gas containing a chlorinated organic compound, usually 0.1 ppm or more of NO x , usually 0.1 ppm or more of SO x , for example, municipal waste or industrial waste Exhaust gas and the like when a substance or the like is burned. In such a combustion exhaust gas, the above dioxins and coplanar PCBs together with moisture and oxygen are contained in an amount of 0.1 to 200 ng / m 3 (NTP).
(Equivalent value of toxicity) is included. Furthermore, as mentioned above,
Various chlorinated organic compounds that are precursors of dioxins are also included.
【００５７】上記の燃焼排ガスは、通常、バッグフィル
ターに通じて粉塵や重金属などを除去した後に接触工程
に導入される。また、必要に応じ、バッグフィルターで
処理する前に消石灰反応塔で処理して酸性ガスを除去し
てもよい。The above-mentioned combustion exhaust gas is usually introduced into a contact step after passing through a bag filter to remove dust and heavy metals. Further, if necessary, the acid gas may be removed by treating in a slaked lime reaction tower before treating with a bag filter.
【００５８】本発明において、低酸化性能触媒との接触
工程を先行させる場合、低酸化性能触媒との接触工程に
流入する燃焼排ガス中にアンモニアを導入するが、その
量は当該工程から流出する燃焼排ガス中のアンモニア濃
度が２０ｐｐｍ以下となる量に調節する。In the present invention, when the step of contacting with the catalyst having a low oxidizing performance is preceded, ammonia is introduced into the combustion exhaust gas flowing into the step of contacting with the catalyst having a low oxidizing performance. The amount is adjusted so that the ammonia concentration in the exhaust gas becomes 20 ppm or less.
【００５９】すなわち、上記の場合、第１工程である低
酸化性能触媒との接触工程は、窒素酸化物の分解のた
め、アンモニアの存在下に行う。この際、酸性硫酸アン
モニウムは、触媒が低酸化性であるため、殆ど生成しな
い。従って、窒素酸化物の分解と同時に、塩素化有機化
合物は、低酸化性能触媒の能力に応じた高い水準で分解
される。燃焼排ガス中へのアンモニアの導入量は、上記
の条件下、窒素酸化物を高分解し得る様に決定される。
なお、燃焼排ガス中でのアンモニアの消費量は、燃焼排
ガスの温度および処理量、触媒の使用量およびガス接触
面積などで決定される。上記の第１工程から流出する燃
焼排ガス中に残存する塩素化有機化合物は、第２工程で
ある高酸化性能触媒との接触工程によって分解される。
この際、酸性硫酸アンモニウムは、燃焼排ガス中のアン
モニア濃度が２０ｐｐｍ以下に抑えられているため、殆
ど生成しない。That is, in the above case, the first step of contacting with the low oxidation performance catalyst is performed in the presence of ammonia to decompose nitrogen oxides. At this time, ammonium acid sulfate is hardly generated because the catalyst has low oxidizing property. Therefore, at the same time as the decomposition of the nitrogen oxides, the chlorinated organic compounds are decomposed at a high level corresponding to the capacity of the low oxidation performance catalyst. The amount of ammonia introduced into the combustion exhaust gas is determined so that nitrogen oxides can be highly decomposed under the above conditions.
The amount of consumption of ammonia in the flue gas is determined by the temperature and the amount of the flue gas, the amount of the catalyst used, the gas contact area, and the like. The chlorinated organic compound remaining in the combustion exhaust gas flowing out of the first step is decomposed in the second step, a step of contacting with a high oxidation performance catalyst.
At this time, almost no ammonium ammonium sulfate is generated because the ammonia concentration in the combustion exhaust gas is suppressed to 20 ppm or less.
【００６０】一方、本発明に係る燃焼排ガスの処理方法
において、高酸化性能触媒との接触工程を先行させる場
合、低酸化性能触媒との接触工程に流入する燃焼排ガス
中にアンモニアを導入する。On the other hand, in the method for treating combustion exhaust gas according to the present invention, when the step of contacting with the catalyst having high oxidation performance is preceded, ammonia is introduced into the combustion exhaust gas flowing into the step of contacting with catalyst having low oxidation performance.
【００６１】すなわち、上記の場合、第１工程である高
酸化性能触媒との接触工程は、塩素化有機化合物の分解
を行い、実質的に窒素酸化物の分解を行わないためアン
モニアの不存在下に行う。なお、窒素酸化物の一部分解
のため焼却炉内にアンモニアを導入している場合は、燃
焼排ガス中のアンモニア濃度が２０ｐｐｍ以下となる様
に焼却炉内に導入するアンモニア量を調節する。上記の
第１工程から流出する燃焼排ガス中の窒素酸化物は、第
２工程である低酸化性能触媒との接触工程によって分解
される。この際、酸性硫酸アンモニウムは、触媒が低酸
化性であるため、殆ど生成しない。従って、低酸化性能
触媒との接触工程に流入する燃焼排ガス（上記の第１工
程からの流出ガス）中に導入されるアンモニアの量は、
窒素酸化物を高分解し得る様に任意に決定される。That is, in the above case, the first step, the step of contacting with the high oxidation performance catalyst, decomposes the chlorinated organic compound and does not substantially decompose nitrogen oxides, so that in the absence of ammonia. To do. When ammonia is introduced into the incinerator for partial decomposition of nitrogen oxides, the amount of ammonia introduced into the incinerator is adjusted so that the ammonia concentration in the combustion exhaust gas becomes 20 ppm or less. Nitrogen oxides in the combustion exhaust gas flowing out of the first step are decomposed in the second step, a step of contacting with a low oxidation performance catalyst. At this time, ammonium acid sulfate is hardly generated because the catalyst has low oxidizing property. Therefore, the amount of ammonia introduced into the combustion exhaust gas (outflow gas from the above-mentioned first step) flowing into the contact step with the low oxidation performance catalyst is:
It is arbitrarily determined so that nitrogen oxides can be highly decomposed.
【００６２】上記の各接触工程における反応器の大きさ
及び形状は、本発明の目的を逸脱しない限り、任意に選
択することが出来る。また、各触媒は、別々の反応器に
充填しても、同一の反応器に異なる層として充填しても
よい。The size and shape of the reactor in each of the above contacting steps can be arbitrarily selected without departing from the object of the present invention. Further, each catalyst may be charged in a separate reactor or may be charged in the same reactor as different layers.
【００６３】[0063]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明はその要旨を超えない限り、以下の実施例に
より限定されるものではない。なお、以下の諸例で使用
した触媒（Ａ）〜（Ｆ）は次の様に調製した。EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The catalysts (A) to (F) used in the following examples were prepared as follows.
【００６４】＜ＳｉＯ2−ＴｉＯ2２元系複合酸化物の調
製（１）＞硫酸法による酸化チタンの製造工程より得ら
れる硫酸チタン溶液を熱加水分解してメタチタン酸を
得、これを酸化チタンとして８００ｇ取り出し、還流器
付撹拌槽に仕込み、これに１５重量％アンモニア水４９
８ｇを加えてｐＨを９．５に調整した後、９５℃にて１
時間に亘り十分な撹拌を行いつつ加熱熟成した。次い
で、シリカゾル（触媒化成社製「キャタロイドＳ−２０
Ｌ）２１１ｇを添加し、更に、上記と同一条件の加熱熟
成を１時間行なった。その後、冷却してスラリーを取り
出し、濾過脱水し、得られたケーキを１００℃で２０時
間乾燥した後、６００℃まで７５℃／Ｈｒの速度で昇温
し、同温度で５時間保持した。そして、冷却後、適当な
粒度に粉砕し、ＳｉＯ2／ＴｉＯ2比が５重量％／９５重
量％の、ＳｉＯ2−ＴｉＯ2２元系複合酸化物を得た。[0064] to obtain a metatitanic acid <Preparation of SiO 2 -TiO 2 2-element compound oxide (1)> to the titanium sulphate solution obtained from the manufacturing process of titanium oxide by sulfuric acid method and thermal hydrolysis, titanium oxide which 800 g, and charged to a stirring tank equipped with a reflux condenser.
After adjusting the pH to 9.5 by adding 8 g, 1
Heat aging was performed with sufficient stirring over time. Then, a silica sol ("Cataloid S-20" manufactured by Kasei Kasei Co., Ltd.)
L) 211 g was added, and heat aging under the same conditions as above was performed for 1 hour. After cooling, the slurry was taken out, filtered and dewatered, and the obtained cake was dried at 100 ° C. for 20 hours, heated to 600 ° C. at a rate of 75 ° C./Hr, and kept at the same temperature for 5 hours. After cooling, the mixture was pulverized to an appropriate particle size to obtain a SiO 2 -TiO 2 binary composite oxide having a SiO 2 / TiO 2 ratio of 5% by weight / 95% by weight.
【００６５】＜ＳｉＯ2−ＴｉＯ2２元系複合酸化物の調
製（２）＞上記の調製（１）において、酸化チタンとシ
リカゾルの使用量を変えた以外は、同様の方法により、
ＳｉＯ2／ＴｉＯ2比が１５重量％／８５重量％の、Ｓｉ
Ｏ 2−ＴｉＯ2２元系複合酸化物粉末を得た。<SiOTwo-TiOTwoPreparation of binary composite oxide
(2)> In the above preparation (1), titanium oxide and silicon
Except for changing the amount of licazol,
SiOTwo/ TiOTwoSi with a ratio of 15% by weight / 85% by weight
O Two-TiOTwoA binary composite oxide powder was obtained.
【００６６】＜触媒の調製＞ 触媒（Ａ）の調製：メタバナジン酸アンモニウム１０２
９ｇとパラモリブデン酸アンモニウム７３６ｇを８０℃
に加温した１０重量％モノエタノールアミン水溶液６０
００ｇに溶解して原料液（１）を調製した。上記の調製
（１）で得たＳｉＯ2−ＴｉＯ2２元系複合酸化物粉末
（５重量％ＳｉＯ2／９５重量％ＴｉＯ2）１９００ｇと
純粋なＴｉＯ2粉末５７００ｇとを双腕型ニーダーで１
時間に亘り乾式混合し、当該混合物に原料液（１）と成
形助材１０００ｇを加えて更に２時間混練し、得られた
混練物を押出機により口径５ｍｍのハニカム構造に成形
した。得られた成形物を１３０℃の温度で２４時間乾燥
し、次いでＳＶ１００Ｈｒ-1、温度５００℃の条件下で
３時間焼成し、表１に示す触媒（Ａ）を得た。<Preparation of catalyst> Preparation of catalyst (A): ammonium metavanadate 102
9 g and 736 g of ammonium paramolybdate at 80 ° C.
10% by weight aqueous monoethanolamine solution 60
This was dissolved in 00 g to prepare a raw material liquid (1). 1900 g of the SiO 2 —TiO 2 binary composite oxide powder (5% by weight SiO 2 /95% by weight TiO 2 ) obtained in the above preparation (1) and 5700 g of pure TiO 2 powder were mixed in a double-arm kneader.
The mixture was dry-mixed over a period of time, the raw material liquid (1) and 1000 g of a forming aid were added to the mixture, and the mixture was kneaded for another 2 hours. The obtained kneaded product was formed into a honeycomb structure having a diameter of 5 mm by an extruder. The obtained molded product was dried at a temperature of 130 ° C. for 24 hours, and then calcined under a condition of SV100Hr −1 and a temperature of 500 ° C. for 3 hours to obtain a catalyst (A) shown in Table 1.
【００６７】触媒（Ｂ）の調製：上記の触媒（Ａ）の調
製において、メタバナジン酸アンモニウムの使用量を６
４３ｇ、ＳｉＯ2−ＴｉＯ2２元系複合酸化物粉末の使用
量を１９７５ｇ、純粋なＴｉＯ2粉末の使用量を５９２
５ｇにそれぞれ変更した以外は、触媒（Ａ）の調製と同
様にして表１に示す触媒（Ｂ）を得た。Preparation of catalyst (B): In the preparation of catalyst (A), the amount of ammonium metavanadate used was changed to 6
43g, SiO 2 -TiO 2 2-way system 1975g usage of the composite oxide powder, the amount of the pure TiO 2 powder 592
Catalyst (B) shown in Table 1 was obtained in the same manner as in the preparation of catalyst (A), except that the amount was changed to 5 g.
【００６８】触媒（Ｃ）の調製：上記の触媒（Ａ）の調
製において、前記の調製（２）で得たＳｉＯ2−ＴｉＯ2
２元系複合酸化物粉末（１５重量％ＳｉＯ2／８５重量
％ＴｉＯ2）を使用し、その使用量を５０６７ｇとし、
純粋なＴｉＯ2粉末の使用量を２５３３ｇに変更した以
外は、触媒（Ａ）の調製と同様にして表１に示す触媒
（Ｃ）を得た。Preparation of the catalyst (C): In the preparation of the catalyst (A), the SiO 2 —TiO 2 obtained in the preparation (2) was used.
A binary composite oxide powder (15% by weight SiO 2 /85% by weight TiO 2 ) was used, and the amount used was 5067 g.
A catalyst (C) shown in Table 1 was obtained in the same manner as in the preparation of the catalyst (A), except that the amount of the pure TiO 2 powder was changed to 2,533 g.
【００６９】触媒（Ｄ）の調製：上記の触媒（Ａ）の調
製において、原料液（１）にパラモリブデン酸アンモニ
ウムを添加せず、パラタングステン酸アンモニウム１０
７０ｇとメタバナジン酸アンモニウム５１６ｇを添加
し、そして、ＳｉＯ2−ＴｉＯ2２元系複合酸化物粉末を
使用せず、純粋なＴｉＯ2のみを７６５０ｇ使用した以
外は、触媒（Ａ）の調製と同様にして表１に示す触媒
（Ｄ）を得た。Preparation of catalyst (D): In the preparation of catalyst (A) described above, ammonium paramolybdate was not added to raw material liquid (1), and ammonium paratungstate was added.
70 g and 516 g of ammonium metavanadate were added, and the preparation of the catalyst (A) was carried out in the same manner as in the preparation of the catalyst (A), except that 7650 g of pure TiO 2 alone was used without using the SiO 2 —TiO 2 binary composite oxide powder. Thus, a catalyst (D) shown in Table 1 was obtained.
【００７０】触媒（Ｅ）の調製：上記の触媒（Ａ）の調
製において、メタバナジン酸アンモニウムの使用量を１
２９ｇ、パラモリブデン酸アンモニウムの使用量を７４
ｇ、ＳｉＯ2−ＴｉＯ2２元系複合酸化物粉末の使用量を
２２１０ｇ、純粋なＴｉＯ2粉末の使用量を６６３０ｇ
にそれぞれ変更したした以外は、触媒（Ａ）の調製と同
様にして表１に示す触媒（Ｅ）を得た。Preparation of catalyst (E): In the preparation of catalyst (A), the amount of ammonium metavanadate used was changed to 1
29 g, the amount of ammonium paramolybdate used was 74
g, SiO 2 -TiO 2 2-way system 2210g usage of the composite oxide powder, the amount of the pure TiO 2 powder 6630g
The catalyst (E) shown in Table 1 was obtained in the same manner as in the preparation of the catalyst (A), except that the catalyst was changed respectively.
【００７１】触媒（Ｆ）の調製：上記の触媒（Ａ）の調
製において、メタバナジン酸アンモニウムの使用量を６
４３ｇ、ＳｉＯ2−ＴｉＯ2２元系複合酸化物粉末の使用
量を７９００ｇに変更し、純粋なＴｉＯ2粉末を使用し
ない以外は、触媒（Ａ）の調製と同様にして表１に示す
触媒（Ｆ）を得た。Preparation of catalyst (F): In the preparation of catalyst (A), the amount of ammonium metavanadate used was changed to 6
The catalysts shown in Table 1 were prepared in the same manner as in the preparation of the catalyst (A) except that the amount of the SiO 2 —TiO 2 binary composite oxide powder was changed to 7900 g and pure TiO 2 powder was not used. F) was obtained.
【００７２】＜二酸化イオウ酸化転化率の測定＞前記の
触媒の内、（Ａ）、（Ｂ）、（Ｄ）及び（Ｅ）をそれぞ
れ４５０ｍｌ（縦および横方向に夫々６個の孔を有し且
つ高さが５００ｍｍのハニカム構造）のサンプルに加工
して石英ガラス製の反応管に充填した。次いで、管状型
電気炉に反応管を入れ、窒素ガスと酸素ガスを所定量流
通させながら触媒の温度を２５０℃に保持した。次い
で、所定濃度となる様にＨ2ＯとＳＯ2ガスを添加した。
ガス組成は、Ｏ2１０乾体積%，ＳＯ2５００ｐｐｍ，Ｈ2
Ｏ１０体積%，Ｎ2バランス量であり、ガス調製量（速
度）は８３５Ｌ／Ｈｒ（ａｔ ０℃，１０１．３２５Ｋ
Ｐａ）とした。<Measurement of Sulfur Dioxide Oxidation Conversion Ratio> Of the above catalysts, (A), (B), (D) and (E) were each 450 ml (having 6 holes each in the vertical and horizontal directions). The sample was processed into a sample having a honeycomb structure with a height of 500 mm) and filled in a quartz glass reaction tube. Next, the reaction tube was placed in a tubular electric furnace, and the temperature of the catalyst was maintained at 250 ° C. while flowing a predetermined amount of nitrogen gas and oxygen gas. Next, H 2 O and SO 2 gas were added to a predetermined concentration.
The gas composition was O 2 10 dry volume%, SO 2 500 ppm, H 2
O 10% by volume, N 2 balance amount, gas preparation amount (rate) is 835 L / Hr (at 0 ° C., 101.325 K
Pa).
【００７３】前記の反応管に上記のガスを７０時間通過
させ、その後、反応管の出口のガスをサンプリングしＳ
Ｏ3濃度を測定した。次いで、再度、反応管の出口のガ
スをサンプリングしトータルＳＯX濃度を測定した。Ｓ
Ｏ3のサンプリングはスパイラル管式捕集管を使用して
ＳＯXの内ＳＯ3のみを捕集することによって行った。そ
して、捕集したＳＯ3は、水で洗い採り、ＪＩＳ Ｋ
０１０３の沈殿滴定法にて分析した。トータルＳＯXの
サンプリング及び分析は、ＪＩＳ Ｋ ０１０３の方法
によって行った。二酸化イオウの酸化転化率は次式によ
り求めた。The above gas was passed through the reaction tube for 70 hours. Thereafter, the gas at the outlet of the reaction tube was sampled and
The O 3 concentration was measured. Next, the gas at the outlet of the reaction tube was sampled again to measure the total SO X concentration. S
Sampling of O 3 was performed by collecting only SO 3 of SO X using a spiral tube type collection tube. Then, the collected SO 3 is washed out with water, and JIS K
The analysis was performed by the precipitation titration method of No. 0103. Sampling and analysis of total SO X were performed according to the method of JIS K0103. The oxidation conversion of sulfur dioxide was determined by the following equation.
【００７４】[0074]
【数４】 （出口ＳＯ3濃度／出口トータルＳＯX）×１００[Equation 4] (Outlet SO 3 concentration / Outlet total SO X ) × 100
【００７５】[0075]
【表１】 [Table 1]
【００７６】＜活性試験−１＞ガラス製反応器に上記の
各触媒を３０ｍｌ充填し、常圧固定床流通反応装置で活
性試験を行なった。触媒固定床の寸法は、縦２８ｍｍ、
横２８ｍｍ、高さ３８ｍｍであった。原料ガス組成は、
オルトクロルフェノール（ＯＣＰ）１００ｐｐｍ、Ｏ2
１０ｖｏｌ％、Ｈ2Ｏ１０ｖｏｌ％、Ｎ2バランス量の組
成であった。原料ガスのＳＶは５０００Ｈｒ-1であっ
た。１６０℃と１８０℃の各温度で５時間保持した後、
反応装置通過ガスをマイクロシリンジでサンプリング
し、ガスクロマトグラフィーで分析した。分析は絶対検
量線法で行なった。<Activity Test-1> A glass reactor was charged with 30 ml of each of the above catalysts, and an activity test was carried out using a normal pressure fixed bed flow reactor. The size of the fixed catalyst bed is 28 mm long,
It was 28 mm wide and 38 mm high. The raw gas composition is
Orthochlorophenol (OCP) 100 ppm, O 2
The composition was 10 vol%, H 2 O 10 vol%, and N 2 balance amount. The SV of the raw material gas was 5000 Hr -1 . After holding at 160 ° C. and 180 ° C. for 5 hours,
The gas passing through the reactor was sampled with a microsyringe and analyzed by gas chromatography. The analysis was performed by the absolute calibration method.
【００７７】＜活性試験−２＞ガラス製反応器に上記の
各触媒を３０ｍｌ充填し、常圧固定床流通反応装置で活
性試験を行なった。触媒固定床の寸法は、縦２８ｍｍ、
横２８ｍｍ、高さ３８ｍｍであった。原料ガス組成は、
モノクロルベンゼン（ＭＣＢ）１００ｐｐｍ、Ｏ2１０
ｖｏｌ％、Ｈ2Ｏ１０ｖｏｌ％、Ｎ2バランス量の組成で
あった。原料ガスのＳＶは３０００Ｈｒ-1であった。１
６０℃と１８０℃の各温度で５時間保持した後、反応装
置通過ガスをマイクロシリンジでサンプリングし、ガス
クロマトグラフィーで分析した。分析は絶対検量線法で
行なった。<Activity Test-2> A glass reactor was charged with 30 ml of each of the above catalysts, and an activity test was carried out in a fixed-bed flow reactor under normal pressure. The size of the fixed catalyst bed is 28 mm long,
It was 28 mm wide and 38 mm high. The raw gas composition is
Monochlorobenzene (MCB) 100 ppm, O 2 10
The composition was a vol%, H 2 O 10 vol%, and N 2 balance amount. The SV of the raw material gas was 3000 Hr -1 . 1
After maintaining at 60 ° C. and 180 ° C. for 5 hours, the gas passing through the reactor was sampled by a microsyringe and analyzed by gas chromatography. The analysis was performed by the absolute calibration method.
【００７８】実施例１及び２ 触媒（Ａ）及び（Ｂ）を使用して活性試験−１を行なっ
た。その結果を表２に示す。Examples 1 and 2 Activity test-1 was carried out using catalysts (A) and (B). Table 2 shows the results.
【００７９】実施例３ 触媒（Ａ）を使用して活性試験−２を行なった。その結
果を表３に示す。Example 3 An activity test-2 was carried out using the catalyst (A). Table 3 shows the results.
【００８０】比較例１及び２ 触媒（Ｃ）及び（Ｄ）を使用して活性試験−１を行なっ
た。その結果を表２に示す。Comparative Examples 1 and 2 Activity test-1 was carried out using catalysts (C) and (D). Table 2 shows the results.
【００８１】比較例３ 触媒（Ｆ）を使用して活性試験−２を行なった。その結
果を表３に示す。Comparative Example 3 An activity test-2 was carried out using the catalyst (F). Table 3 shows the results.
【００８２】実施例４ 触媒（Ｂ）を使用して活性試験−２を行なった。その結
果を表３に示す。Example 4 An activity test-2 was carried out using the catalyst (B). Table 3 shows the results.
【００８３】比較例４ 触媒（Ｃ）を使用して活性試験−２を行なった。その結
果を表３に示す。Comparative Example 4 Activity test-2 was carried out using the catalyst (C). Table 3 shows the results.
【００８４】[0084]
【表２】 [Table 2]
【００８５】[0085]
【表３】 [Table 3]
【００８６】実施例５ ３ｃｍ×３ｃｍ×５０ｃｍのハニカム構造の触媒を充填
した内径５ｃｍ、長さ６０ｃｍのガラス製反応器を３本
直列に接続し、縦内径８０ｃｍ、横内径８０ｃｍ、高さ
１．５ｍの恒温槽内に設置した。前２本の反応器に触媒
（Ｅ）、後１本の反応器に触媒（Ａ）を充填して常圧固
定床流通反応装置を組み立てた。そして、この装置を使
用し、都市ゴミ焼却炉のモデル排ガスの処理試験を次の
要領で行った。Example 5 Three glass reactors each having a size of 3 cm × 3 cm × 50 cm and filled with a catalyst having a honeycomb structure and having an inner diameter of 5 cm and a length of 60 cm were connected in series, and a vertical inner diameter of 80 cm, a horizontal inner diameter of 80 cm and a height of 1. It was installed in a 5 m constant temperature bath. The catalyst (E) was charged into the first two reactors and the catalyst (A) was charged into the last two reactors to assemble a normal pressure fixed bed flow reactor. Using this apparatus, a treatment test of a model exhaust gas from a municipal waste incinerator was performed as follows.
【００８７】温度１８０℃、ＳＶ５０００Ｈｒ-1の条件
下、平均濃度８０ｐｐｍのアンモニアを添加しながら、
上記の装置に、平均濃度１ｎｇ−ＴＥＱ／ｍ3（Ｎ．
Ｔ．Ｐ）のダイオキシン類と平均濃度３０ｐｐｍのＳＯ
2と平均濃度７５ｐｐｍのＮＯxを含有するガスを通過さ
せた。アンモニアの添加量は、触媒（Ａ）の直前（前２
本の反応器の直後）のアンモニア濃度を測定し、その値
が２０ｐｐｍ以下となる様に調節した。At a temperature of 180 ° C. and an SV of 5000 Hr −1 , while adding ammonia having an average concentration of 80 ppm,
An average concentration of 1 ng-TEQ / m 3 (N.
T. P) Dioxins and SO with an average concentration of 30 ppm
2 and passed through a gas containing an average concentration 75ppm of NO x. The amount of ammonia added is determined immediately before the catalyst (A).
The ammonia concentration (just after this reactor) was measured and adjusted so that the value was 20 ppm or less.
【００８８】処理後の排ガスの分析は、ガスクロマトグ
ラフィー質量分析法で「廃棄物処理におけるダイオキシ
ン類標準測定分析マニュアル」（厚生省生活衛生局水道
環境部環境整備課（平成９年２月））に準じて行った。
分析は通ガス後２週間後と４ヶ月後に行った。評価結果
を表４に示す。The exhaust gas after treatment was analyzed by gas chromatography mass spectrometry according to the “Standard Manual for Analysis and Analysis of Dioxins in Waste Disposal” (Environmental Improvement Division, Water Environment Department, Ministry of Health and Welfare, Ministry of Health and Welfare, February 1997). I went according to.
The analysis was performed two weeks and four months after passing the gas. Table 4 shows the evaluation results.
【００８９】実施例６ 実施例５において、常圧固定床流通反応装置を組み立て
る際、前１本に触媒（Ａ）、後２本に触媒（Ｅ）を充填
した。そして、アンモニアの添加位置を触媒（Ｅ）の直
前（前１本の直後）とし、アンモニア添加量を平均ＮＯ
ｘ濃度に対し、モル比（ＮＯx／ＮＨ3）で１とした以外
は、実施例５と同様にして都市ゴミ焼却炉のモデル排ガ
スの処理試験を行った。評価結果を表５に示す。Example 6 In Example 5, when assembling a normal-pressure fixed-bed flow reactor, one catalyst was charged at the front and two catalysts (E) were charged at the rear. Then, the ammonia addition position is set immediately before the catalyst (E) (immediately after the previous one), and the ammonia addition amount is set to the average NO.
x concentration relative, except for using 1 molar ratio (NO x / NH 3), was subjected to treatment test model exhaust gas of municipal waste incinerators in the same manner as in Example 5. Table 5 shows the evaluation results.
【００９０】比較例５ 実施例５において、全３本に触媒（Ｄ）を使用して組み
立てた常圧固定床流通反応装置を使用し、温度を２００
℃に変更し、そして、前２本直後のアンモニア濃度の測
定結果に基づくアンモニア添加量の調節を行なわなかっ
たこと以外は、実施例５と同様な方法でモデル排ガスの
処理試験を行なった。評価結果を表６に示す。Comparative Example 5 In Example 5, an atmospheric pressure fixed bed flow reactor assembled using the catalyst (D) for all three was used, and the temperature was 200
° C, and a model exhaust gas treatment test was performed in the same manner as in Example 5, except that the amount of added ammonia was not adjusted based on the measurement results of the ammonia concentration immediately after the previous two tubes. Table 6 shows the evaluation results.
【００９１】[0091]
【表４】 [Table 4]
【００９２】[0092]
【表５】 [Table 5]
【００９３】[0093]
【表６】 [Table 6]
【００９４】[0094]
【発明の効果】以上説明した本発明によれば、ＳｉＯ2
−ＴｉＯ2２元系複合酸化物と純粋なＴｉＯ2とから成る
担体を使用した触媒により、より低温度でダイオキシン
等の塩素化有機化合物を高効率で分解することが出来
る。また、本発明によれば、一旦分解されたダイオキシ
ン等が再生成することがない。更に、本発明によれば、
硫黄酸化物から生成する酸性硫酸アンモニウムを極力少
なくすることにより、触媒の経時的性能劣化が抑制され
るため、燃焼排ガス中のダイオキシン等の塩素化有機化
合物および窒素酸化物を高効率で除去することが出来
る。According to the present invention described above, SiO 2
-TiO 2 by 2-way catalysts using a carrier consisting of composite oxide and the pure TiO 2 Prefecture, chlorinated organic compounds such as dioxin can be decomposed with high efficiency at a lower temperature. Further, according to the present invention, once decomposed dioxin or the like does not regenerate. Further, according to the present invention,
By minimizing the amount of ammonium ammonium sulfate generated from sulfur oxides, deterioration of catalyst performance over time is suppressed, so chlorinated organic compounds such as dioxins and nitrogen oxides in flue gas can be removed with high efficiency. I can do it.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｂ 35/06 Ｃ０７Ｄ 319/24 37/06 Ｂ０１Ｄ 53/36 ＺＡＢＧ Ｃ０７Ｃ 25/18 Ｄ // Ｃ０７Ｄ 319/24 １０２Ｂ (72)発明者 清野 健一 三重県四日市市東邦町１番地 三菱化学株 式会社四日市事業所内 (72)発明者 内田 雅昭 福岡県北九州市若松区北湊町13番２号 触 媒化成工業株式会社若松工場内 (72)発明者 足立 健太郎 福岡県北九州市若松区北湊町13番２号 触 媒化成工業株式会社若松工場内 (72)発明者 西井 一博 東京都港区芝五丁目34番６号 三菱化学エ ンジニアリング株式会社内 Ｆターム(参考） 4D048 AA02 AA06 AA11 AB03 AC04 BA06X BA07X BA17Y BA18Y BA19Y BA23X BA25Y BA26X BA27Y BA28Y BA31Y BA33Y BA34Y BA35Y BA36Y BA38Y BA41X BA42X BB02 CC32 CC39 CC46 CC61 CD03 DA03 DA06 DA09 4G069 AA01 AA03 AA08 BA02A BA02B BA04A BA04B BB02A BB04A BB04B BB06A BB06B BC18A BC31A BC32A BC33A BC40A BC43A BC44A BC54A BC54B BC58A BC59A BC59B BC60A BC62A BC66A BC68A BC72A BC74A CA02 CA10 CA12 CA13 CA19 DA06 EA18 EC26 EC27 FA02 FA03 FB06 FB08 FB67 FC08 4H006 AA05 AC13 AC26 BA05 BA08 BA09 BA12 BA14 BA16 BA19 BA21 BA22 BA25 BA30 BA55 BC10 EA22 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C07B 35/06 C07D 319/24 37/06 B01D 53/36 ZABG C07C 25/18 D // C07D 319/24 102B (72) Inventor Kenichi Seino 1 Tohocho, Yokkaichi-shi, Mie Prefecture Inside Yokkaichi Office of Mitsubishi Chemical Corporation (72) Inventor Masaaki Uchida 13-2 Kitaminato-machi, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Inside the plant (72) Inventor Kentaro Adachi 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Inside the Wakamatsu plant of Catalyst Chemicals Co., Ltd. (72) Inventor Kazuhiro Nishi 5-34-6 Shiba, Minato-ku, Tokyo Mitsubishi F-term in Chemical Engineering Co., Ltd. (reference) 4D048 AA02 AA06 AA11 AB03 AC04 BA06X BA07X BA17Y BA18Y BA19Y BA23X BA25Y BA26X BA27Y BA28Y BA31 Y BA33Y BA34Y BA35Y BA36Y BA38Y BA41X BA42X BB02 CC32 CC39 CC46 CC61 CD03 DA03 DA06 DA09 4G069 AA01 AA03 AA08 BA02A BA02B BA04A BA04B BB02A BB04A BB04B BB06A BB06B BC18A BCBC BCA BC31A BC32A BC40 BC CA12 CA13 CA19 DA06 EA18 EC26 EC27 FA02 FA03 FB06 FB08 FB67 FC08 4H006 AA05 AC13 AC26 BA05 BA08 BA09 BA12 BA14 BA16 BA19 BA21 BA22 BA25 BA30 BA55 BC10 EA22
Claims (7)
させる塩素化有機化合物の分解方法において、担体に活
性成分が担持された触媒であって、担体がＳｉＯ2−Ｔ
ｉＯ2２元系複合酸化物とＴｉＯ2から成り且つ両者の全
量に対する前者の割合が５０重量％以下である混合物か
ら成る触媒を使用することを特徴とする塩素化有機化合
物の分解方法。1. A method for decomposing a chlorinated organic compound in which a gas containing a chlorinated organic compound is brought into contact with a catalyst, the catalyst comprising an active ingredient supported on a carrier, wherein the carrier is SiO 2 -T
method for decomposing the chlorinated organic compound ratio of the former against iO 2 2-element complex oxide and and both the total amount consists of TiO 2 is characterized by the use of a catalyst comprising a mixture of 50 wt% or less.
の分解方法。2. The decomposition method according to claim 1, wherein the SiO 2 is amorphous.
ｉＯ2から成る混合物において、ＳｉＯ2の割合が０．５
〜３重量％であり、残余がＴｉＯ2である請求項１又は
２に記載の分解方法。3. An SiO 2 —TiO 2 binary composite oxide and T
In the mixture consisting of iO 2 , the proportion of SiO 2 is 0.5
The decomposition method according to claim 1, wherein the content is 〜3% by weight, and the balance is TiO 2 .
ｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ａｇ、Ａｕ、Ｐｄ、Ｙ、Ｃｅ、
Ｎｄ、Ｗ、Ｉｎ及びＩｒの群から選ばれる少なくとも１
種の金属および／またはその酸化物である請求項１〜３
の何れかに記載の分解方法。4. The catalyst according to claim 1, wherein the active components are V, Cr, Mo, M
n, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce,
At least one selected from the group consisting of Nd, W, In and Ir
4. A metal and / or an oxide thereof.
The decomposition method according to any one of the above.
デンの複合酸化物を含有する請求項１〜４の何れかに記
載の分解方法。5. The decomposition method according to claim 1, wherein the active component of the catalyst contains a composite oxide of vanadium and molybdenum.
触温度が１００〜２５０℃である請求項１〜６の何れか
に記載の分解方法。6. The decomposition method according to claim 1, wherein the contact temperature between the chlorinated organic compound-containing gas and the catalyst is 100 to 250 ° C.
素酸化物を含有する燃焼排ガスの処理方法であって、次
の（ａ）〜（ｄ）の条件を満足することを特徴とする燃
焼排ガスの処理方法。 （ａ）触媒として、塩素化有機化合物分解能とアンモニ
ア存在下における窒素酸化物分解能とを有し且つ以下に
規定する二酸化イオウの酸化転化率が１．３%以下の低
酸化性能触媒（Ｘ）と、担体に活性成分が担持された触
媒であって、担体として、ＳｉＯ2−ＴｉＯ2２元系複合
酸化物とＴｉＯ2から成り且つ両者の全量に対する前者
の割合が５０重量％以下である混合物が使用され、しか
も、塩素化有機化合物分解能を有し且つ以下に規定する
二酸化イオウの酸化転化率が３．０%以上の高酸化性能
触媒（Ｙ）との２種類を使用する。 ＜二酸化イオウの酸化転化率＞圧力：常圧、温度：２５
０℃、ＳＶ（空間速度）：１８５０Ｈｒ-1、触媒量：４
５０ｍｌの条件下、Ｏ2１０乾体積%，ＳＯ2５００ｐｐ
ｍ，Ｈ2Ｏ：１０体積%，Ｎ2バランス量の組成のガスを
触媒が充填された反応管に供給し、反応管出口のＳＯ3
濃度とトータルＳＯXの濃度を求め、次式により二酸化
イオウの酸化転化率（%）を算出する。 【数１】 （出口ＳＯ3濃度／出口トータルＳＯX）×１００ （ｂ）燃焼排ガスと低酸化性能触媒および高酸化性能触
媒との各接触工程を任意の順序で且つ１００〜２５０℃
の温度範囲で行う。 （ｃ）低酸化性能触媒との接触工程を先行させる場合、
低酸化性能触媒との接触工程に流入する燃焼排ガス中に
アンモニアを導入するが、その量は当該工程から流出す
る燃焼排ガス中のアンモニア濃度が２０ｐｐｍ以下とな
る量に調節する。 （ｄ）高酸化性能触媒との接触工程を先行させる場合、
低酸化性能触媒との接触工程に流入する燃焼排ガス中に
アンモニアを導入する。7. A method for treating a combustion exhaust gas containing a chlorinated organic compound, sulfur dioxide and nitrogen oxide, wherein the method satisfies the following conditions (a) to (d): Processing method. (A) a low oxidation performance catalyst (X) having a chlorinated organic compound resolution and a nitrogen oxide resolution in the presence of ammonia and having an oxidation conversion of sulfur dioxide of 1.3% or less as defined below. A catalyst in which an active ingredient is supported on a carrier, wherein the carrier is a mixture comprising a SiO 2 —TiO 2 binary composite oxide and TiO 2 , wherein the ratio of the former to the total amount of both is 50% by weight or less. A high oxidation performance catalyst (Y) which is used and has the ability to degrade chlorinated organic compounds and has an oxidation conversion of sulfur dioxide of 3.0% or more as defined below is used. <Oxidation conversion of sulfur dioxide> Pressure: normal pressure, temperature: 25
0 ° C., SV (space velocity): 1850 Hr −1 , amount of catalyst: 4
Under the condition of 50 ml, O 2 10 dry volume%, SO 2 500 pp
A gas having a composition of m, H 2 O: 10% by volume and N 2 balance amount is supplied to the reaction tube filled with the catalyst, and SO 3 at the outlet of the reaction tube is supplied.
The concentration and the total SO X concentration are determined, and the oxidation conversion (%) of sulfur dioxide is calculated by the following equation. ## EQU1 ## (Outlet SO 3 concentration / Outlet total SO X ) × 100 (b) Each contact step between the combustion exhaust gas and the low oxidizing performance catalyst and the high oxidizing performance catalyst is performed in an arbitrary order at 100 to 250 ° C.
The temperature range is as follows. (C) When prior to the contacting step with the low oxidation performance catalyst,
Ammonia is introduced into the flue gas flowing into the contact step with the low oxidation performance catalyst, and the amount is adjusted so that the ammonia concentration in the flue gas flowing out from the step becomes 20 ppm or less. (D) When prior to the contacting step with the high oxidation performance catalyst,
Ammonia is introduced into the combustion exhaust gas flowing into the contact step with the low oxidation performance catalyst.
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|---|---|---|---|---|
| JP2019072663A (en) * | 2017-10-16 | 2019-05-16 | 株式会社日本触媒 | Method for producing organic composite oxide and method for treating exhaust gas using the same |
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|---|---|---|---|---|
| JP2019072663A (en) * | 2017-10-16 | 2019-05-16 | 株式会社日本触媒 | Method for producing organic composite oxide and method for treating exhaust gas using the same |
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